Packaged explosive

ABSTRACT

A skin-tight explosive not having an air space or sag, and a method of making it. An explosive containing a plasticizerextractor is placed in a flexible polyvinyl chloride bag which has been plasticized with an extractable plasticizer. The air space or sagging bag which would normally form is eliminated due to the shrinkage of the bag.

1% ties atent n 1 Slawinski 51 May 8,1973

[54] PACKAGED EXPLOSIVE [75] Inventor: Frank E. Slawlnski, Tamaqua, Pa.

[73] Assignee: ICI America Inc.

[22] Filed: May 14, 1971 [21] App1.No.: 143,328

[52] 11.8. CI. ..102/24 R [51] Int. Cl ..F42b 3/00 [58] Field of Search ..102/24 R [56] References Cited UNITED STATES PATENTS 3,049,079 8/1962 Eilo ..102/24 R 3,342,132 9/1967 Partridge ....102/24 R 3,472,166 10/1969 Dowling ....102/24 R 3,504,628 4/1970 Pack et a1. ..102/24 R FOREIGN PATENTS OR APPLICATIONS OTHER PUBLICATIONS Materials Handbook, George S. Brady, Ninth Ed. 1963, McGraw-I-Iill TA403 B75 1963 C2 page 709 Prir nary Examiner-Verlin R. Pendegrass Attorney-Kenneth E. Mulford and Roger R. Horton 57 ABSTRACT A skin-tight explosive not having an air space or sag, and a method of making it. An explosive containing a plasticizer-extractor is placed in a flexible polyvinyl chloride bag which has been plasticized with an extractable plasticizer. The air space or sagging bag which would normally form is'eliminated due to the shrinkage of'the bag.

15 Claims, 1 Drawing Figure 4/1970 Great Britain ..102/24 R FMENTEUMY 31731 $25 INVENTOR Frank E. Slowinski ATTORNEY PACKAGED EXPLOSIVE Many explosives must be heated during their manufacture. They are usually immediately placed in a package and sealed. This procedure frequently causes the bag to wrinkle and sag or causes an air space to form at the top of the package due to contraction of the explosive as it cools. Anair space or sag may also result due to the rearrangement of particles to mate better as they settle. This frequently happens when AN-FO (ammonium mitrate fuel oil) is packaged, which is done at ambient temperatures. The air space or sag may also be caused by the coalescence of gases dissolved in the explosive or the absorption of gases into solid particles and this, too, may occur at ambient temperatures.

The presence of an air space or sag in the package is unattractive, which makes the product less salable, and an air space may prevent the propagation of the explosion from one container to the next when they are stacked in a borehole.

l have discovered a skin-tight explosive package and a method of making it. Due to an interaction between the container and the explosive, the container shrinks with the explosive forming a skin-tight package with no air space or sag. A flexible polyvinyl chloride (PVC) film is plasticized with an extractable plasticizer and formed into a bag. An explosive which contains a plasticizer-extractor; preferably a solvent for the plasticizer such as most oils, is placed in the bag and the bag is sealed. Gradually, the bag shrinks as the plasticizer in the bag is allowed to be extracted into the plasticizer-extractor in the explosive which may migrate through the plastic to form a light film on the bag.

In addition to the elimination of the air space and sag, the packaged explosive of this invention has superiorelasticity, toughness, and memory which enable it to be dropped into boreholes containing water without rupturing. The shrinkage of the polyvinyl chloride bag also puts pressure on the explosive which may cause the particles in an explosive such as AN-FO to rearrange themselves to give the explosive a higher density. This may be desirable as it will enable'the explosive to sink better in a water-filled borehole.

The accompanying drawing is a side view of a certain presently preferred embodiment of this invention.

In the drawing, a sheet of flexible polyvinyl chloride which has been plasticized with an extractable plasticizer is formed into a tube 1 by making a side lap seal 2. One end of the tube is tied with a cord 3 to form a bag and the bag is filled with an explosive 4 containing a plasticizer-extractor. The other end of the bag is then sealed by tying it with a second cord 5 to form the packaged explosive. 7

While the packaged explosive of FIG. 1 is preferred because of its strength, low cost, and ease of manufacture, other types of bags may also be used. Examples in- The polyvinyl chloride bag is plasticized with a sufficient amount of an extractable plasticizer to l obtain the desired degree of shrinkage when the plasticizer is in part extracted and (2) leave enough plasticizer unextracted to keep the bag flexible. I have found that the amount of plasticizer in the polyvinyl chloride should be about 20 to about percent (all percentages herein are by weight) of the polyvinyl chloride to obtain the best results.

The plasticizer must be extractable. Examples of plasticizers which are extractable in mineral oil and most other oils and are therefore preferred include dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, trichloroethyl phosphate, trioctyl phosphate, tri-Z-ethylhexyl phosphate, octyl-diphenyl phosphate, decyl-diphenyl phosphate, cresyldiphenyl phosphate, tricresyl phosphate, dioctyl adipate, polyethylene glycol di-Z-ethyl-hexoate, and mixtures thereof. Certain alkyl aryl phosphates may also be used. Table 1 gives the percent that various plasticizers were ex tracted from a film after the film was soaked in S.A.E.. 20 oil for 10 days at 23C.

TABLE 1 '7: Extracted The above table was in part obtained from The Stabilization of Polyvinyl Chloride by Chevassus Broutilles, page 263.

Table 2 gives the percent extractability in mineral oil of various phthalate plasticizers. The plasticizer concentrations are at 50 parts per hundred of resin.

TABLE 2 Phthalate 7r Extractable Dioctyl l.0 Diisooctyl 1.3 Diisodecyl 2.4

Various linear phthalates made from Conoco,

Ethyl, and Monsanto alcohols The above table was obtained from the November, 1970 issue of Modern Plastics, page 78.

Table 3 gives the percent extraction of various plasticizers in kerosene. A 40 mil PVC film was used with a plasticizer concentration of 67 p.h.r. (parts per hundred of resin).

TABLE 3 Rustoleum Thinner" 6.3 6.2 7.1 7.6 5.4 7.6 7.1 7.6 Rubtcx 0.4 0.6 1.9 1.2 0.0 0.6 0.8 0.6 g ffl g gg safflower 011 3.6 3.3 5.4 5.0 2.7 3.3 4.4 5.6 I him 67 Soybean Oil 3.1 3.2 4.4 5.0 2.7 3.8 4.4 5.6 gg f gfl 1 Actinol" 3.6 4.4 4.4 5.0 4.0 3.3 4.4 5.0 Y S JS s z 73 5 Turpentine 5.4 6.2 6.3 6.8 5.4 6.2 7.1 7.6 Decyl-diphenyl phosphate 6.7 Cresyl-diphenyl phosphate 2.] Tricresyl phosphate 1.3 l.Texa co. lnc., trademark for lubricating oil. sold y MonsamPichcmicfll CO- under lhc 2. Atlantic Richfield Co. trademark for mineral oil. "ademmk f l 3. Witco Chemical Co. trademark for mineral oil. Sold by under the 4. Texaco. lnc.. trademark for lubricating oil.

trademark Sant1ci1erl48 5. Atlantic Richfield Co. trademark for lubricating oil 6. Rustoleum Corp. trademark for fish oil. The above table was obtained from the Jan. 29, l97 l 7. Texaco, lnc., trademark forlubricating oil. issue f ch page 18 Th diff i 8. Arizona Chemical Co. trademark fora fatty acid fraction oft-all oil. tractability of dioctyl phthalate between Tables 1, 2, and 3 may be due to experimental differences such as Fuel 011, mmeral lubrlcatmg kerosene, the amount of plasticizer originally in the film. nltl'oalkanes from 1 to a and mtroglycerms are At least about 0.1 percent of the plasticizer should be Preferred as y are the most useful in formulating extracted to obtain a noticeable amount of shrinkage. P Preferabl about 3 ercent to about 40 ercent of the p p Table 5 shows the percent contraction of 5" CD by plasticizer 1s extracted to obtam a significant amount of 7 MD sheets of PVC film 1mmersed for various shrinkage wlthout leaving the polyvinyl chlonde bag mo 6 flexibe and brittle penods of time at 70 F. and 90 F. in a mineral Oll sold I r I under the trademark Atreol 34" by the Atlantic Table 4 the page 7 MD Richfield Co. KDA-2030"is UnionCarbides product (machme-dlrectlon) by 5 CD (cross-d1rect1on) sheets of PVC film after 1 Week and 1 month of immersion in designation for 8 m1] PVC plasticlzed with 33.7 percent Various Solvents, primarily oils n is a d1octyl phthalate and having adensity of 1.237 gms./cc.

u n v product designation of Union Carbide for a 12 mil PVC C F 5 product deslgfmted film plasticized with 33.5 percent dioctylphthalate and for 12 ml] PVC Plastlclzed l percent z' having a density of L225 gms./cc. KDA2lO9" is a 30 phthalate and havmg a denslty of 1251 gmS/CC Union Carbide product designation for a 20 mil PVC TOW/rap P S loroduct deslgnanon for film having a density of 1.2l5 gms./cc. plasticized with 24ml Plasnclzed 33.8 percent Flexol lO-l0" (a Carbide and Carbon TABLE Chemicals Co. trademark for diisodecyl phthalat'e).

l Day 3 Days l Week 1 Month TABLE 4 Film 70F 94F 70F 94F 70F 94F 70F 94F KDA-2076" KDA-2109" r 1 Week I Month l Week 1 Month Solvent MD CD MD CD MD CD MD CD KDA-2076 MD 1.4% 1.7% 1.7% 3.6% 3.6%3.6% 4.4% 1 5.3% 40 CD 2.0% 2.0% 1.2%2.4% 2.4%2.4% 5.0% Alcuid Oil 1.3% 1.2% 2.7% 2.6% 0.9%v .2% 1.3%.8% 6.2% A1roo134 2.3 2.6 3.6 3.3 1.9 1.8 2.3 2.6 RDA-2030 MD 1.4% 1.7% 1.7%2.7% 1.7%3.6% 3.6% Klearol, 2.3 2.6 4.0 4.4 1.3 2.6 2.3 3.2 4 4 Castor Oil 2.3 2.6 3.6 3.8 1.9 2.6 3.6 3.8 CD 2,07, 20% 2,4%2,4% 2 4%4 0 7, 50% Cod Liver Oil 1.9 3.8 2.7 5.6 3.6 4.4 5.4 5.0 62% Corn 011 4.4 3.8 5.4 5.0 3.8 KDA-2078 MD 1.4% 1.7% .s6%1.7% 1.7%1.7% 2.7% Corvus" 1.3 1.2 2.3 2.6 0.9 0.6 2.3 2.6 35,7 3230 3 Oil i-Z CD 2.0% 2.0% 1.2%2.4% 1.2%2.4% 2.4% O. r r g y 53-8 32 8-3 -g g8 8-3 8-3 Toywrap MD 3.6% 2.9% 3.6%3.6% 4.4%3.6% 5.3% 2150 "'12 g i 8-8 88 8'8 8% CD 1.2% 2.0% 1.2%2.5% 1.2%2.4% 2.4% 3.8 yco Kerosene 4.4 5.0 6.3 7.6 5.4 5.6 7.1 7.6 Linseed 011 3.6 3.3 5.4 6.2 3.6 5.0 4.4 5.6 Mineral Spirits 6.3 6.2 3.0 8.8 6.3 6.8 7.1 76 Motor Oil No. 10 0.9 1.2 1.9 2.6 0.9 1.2 2.7 2.6 MomrOil 10-30 1.9 1.22.7 2.6 1.3 1.3 1.9 2.6 Table 6 Shows the Percent Contractlo" of y siroglcetgnnuww 9.0 .6 1 51) sheets of PVC film after immersion at F. and l04F. m (7 S for various periods in Atreol 34" mineral oil. 0 (glygerinc) .7 1 0 .0 5:: 5 Regalite is the product designation of Tenneco 1'- '1 .7 fi L3 L8 31 H L3 L8 L8 16 Chemical Co. for a plasticized PVC about 10 mils Peanut Oil 3.1 3.2 4.4 5.0 3.1 4.4 .4 5.0 thick.

W 7 TABLET:

U 1 day, percent 2 days, percent 1 week, percent 2 weeks, percent 1 month, percent '00- PVC x1011 70 F. 104 F. 70 F. 104 F. 70 F. 104 F. 70 F. 104 F. 70 F. 104 F. R0gnlil.v lVlll; 1 g 2 83 1 0 2 83 1 0 4. 43 0. 30 6.20 1.86 6. 20 1 .z. L. a. 2.0 1.2 4.0 2.6 5.0 KDA 2070 0 2. 30 o sq 2 3g 5.523 2.136 7.1 3.6 3.0 x. 2.. 2.6 4.0 ".4 KDA 2030 Mn 0 1.0 0 1.0 1.4 3.0 1.0 5.3 1. 0 0.3 on 1.2 1.2 1.2 1.2 1.2 4.0 2.0 5.0 4.0 6.2

Virtually any explosive containing about 0.1 to about 80 percent extractor for the plasticizer may be used in this invention. Preferably the explosive should contain about 1 percent to about percent plasticizer-extractor in order to extract the plasticizer in amounts previ-' ously described. Dynamite, AN-FO, slurries, and water-in-oil emulsions are four common, suitable explosives which may contain a plasticizer-extractor. usually an oil. Of the four, water-in-oil emulsions are preferred because they exhibit the greatest amount of noticeable product shrinkage and they cause the greatest amount of bag expansion in the polyolefin and copolymer bags commonly used.

A dynamite composition may comprise, for example, 1 pbw (part by weight) inorganic oxidizer salt, about 0.3 to 8 pbw nitroglycerin, nitroglycol, or mixtures thereof, and up to about 0.6 pbw gelatinizing agent such as nitrocotton. Various fuels may also be included. 1

AN-FO compositions contain ammonium nitrate prills and liquid hydrocarbon fuel, for example, about 78 to 97 percent ammonium nitrate and about 2 to 12 percent liquid hydrocarbon fuel, such as fuel oil which is inexpensive. The compositions may also contain surfactants, metals, additional fuels, sensitizers, and other substances.

An oil-containing slurry explosive may comprise, for example, about 10 to about 70 percent inorganic oxidizer salt, about 10 to about 30 percent water, about 1 to 30 percent oil, and sufficient oil thickener to keep the oil from separating. Other fuels, metals, sensitizers, etc., may also be used.

A water-in-oil emulsion explosive may comprise, for example, about 1 to about 10 percent carbonaceous fuel (e.g., an oil), about 55 to about 87 percent ox-' idizer, about 0.1 to about percent sensitizer, about 10 to about percent water, about 1/2 to about 2 percent emulsifier, and sufficient gas to give the explosive a density of about 0.9 to about 1.40 gms./cc. (See Bluhm U. S. Pat. No. 3,447,978).

Table 7 shows the shrinkage and effectiveness of AN-FO explosives in PVC bags after various intervals. The PVC bag used was a side lap sealed bag as shown in the accompanying drawing made from KDA-2076 PVC. Product A is 90 percent whole and ground AN prills, 4 percent No. 2 diesel fuel oil, and 6% al. granules. Product B is 94.25 percent whole Al ground AN prills and 5.75 percent No. 2 diesel fuel oil. The

Table 8 gives the density and velocity when shot of various samples of two water-in-oil emulsion explosives prepared according to Bluhm US. Pat. No. 3,447,978 after various periods of storage at 90F. and ambient temperatures. All samples had a density of 1.15 gms./cc. when prepared. Emulsion A contained 2.5 -percent mineral oil. Emulsion B contained 0.5 percent mineral oil. The samples were shot with 3 highvelocity gelatin primer in 3" X 15" cartridges of K- The above table shows the increase in density of each sample from its original 1.15 gmsjcc.

What is claimed is:

l. A skin-tight packaged explosive composition free of air spaces and sags contained in a sealed, flexible, plasticized polyvinyl chloride film container, said con- .tainer characterized in that a portion of the plasticizer in said polyvinyl chloride film container is extracted by said explosive composition, said explosive composition characterized in that it contains an extractor for said plasticizer in contact with said container.

2. A packaged explosive according to claim 1 wherein said plasticizer is selected from the group con- .sisting of dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, trichloroethyl phosphate, trioctyl phosphate, tri-2-ethylhexyl phosphate, pctyl-diphenyl phosphate, decyl-diphenyl phosphate, cresyl -diphenyl phosphate, tricresyl phosphate, dioctyl Y adipate, polyethylene glycol di-2-ethyl-hexoate, and mixtures thereof.

3. A packaged explosive composition according to claim 1 wherein said explosive is a dynamite.

4. A packaged explosive composition according to claim 1 wherein said explosive composition is AN-FO.

5. A packaged explosive composition according to claim 1 wherein said explosive composition is a slurry.

6. A packaged explosive composition according to claim 1 wherein said explosive composition is a watersamples were shot with 4" high-velocity gelatin in 5" X. in-oil emulsion.

12" cartridges.

7. A packaged explosive composition according to TABLE 7 Product A Product B Time Fresh 1 week 1 month 6 months Fresh 1 week 1 month 6 months Diameter 01 cartridge (inches):

1' 4 1.2. 4 11.1 4 %1 4 9.11 4 2 4 146-1 4 96.1 5 4 %4 1 tto l o 4 9131 4 9114 #5 114 4 5 131 5 4 96.1 5361 4 964 1. 146 1. 184 1.180 1. 20 1. 167 1. 210 1.180 1.177 1. 206 .l- 1.159 1.154 1.14." 1.164 distance from 1 Pnmer' 10, 870 10, 870 10, 20

The above table shows that the cartridge not only claim 1 wherein said polyvinyl chloride film contains shrank but also increased in densityv about 20 to about percent plasticizer.

8. A packaged explosive composition according to claim 1 wherein said container is a lap side sealed bag.

9. A packaged explosive composition according to claim 1 wherein said extractor is a solvent for said plasticizer.

10. A packaged explosive composition according to claim 9 wherein said extractor is an oil.

11. A packaged explosive composition according to claim 9 wherein said solvent is selected from the group consisting of fuel oil, mineral oil, lubricating oil, kerosene, nitroalkanes from C, to C and nitroglycerine.

12. A packaged explosive composition according to 

2. A packaged explosive according to claim 1 wherein said plasticizer is selected from the group consisting of dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, trichloroethyl phosphate, trioctyl phosphate, tri-2-ethylhexyl phosphate, octyl-diphenyl phosphate, decyl-diphenyl phosphate, cresyl-diphenyl phosphate, tricresyl phosphate, dioctyl adipate, polyethylene glycol di-2-ethyl-hexoate, and mixtures thereof.
 3. A packaged explosive composition according to claim 1 wherein said explosive is a dynamite.
 4. A packaged explosive composition according to claim 1 wherein said explosive composition is AN-FO.
 5. A packaged explosive composition according to claim 1 wherein said explosive composition is a slurry.
 6. A packaged explosive composition according to claim 1 wherein said explosive composition is a water-in-oil emulsion.
 7. A packaged explosive composition according to claim 1 wherein said polyvinyl chloride film contains about 20 to about 60 percent plasticizer.
 8. A packaged explosive composition according to claim 1 wherein said container is a lap side sealed bag.
 9. A packaged explosive composition according to claim 1 wherein said extractor is a solvent for said plasticizer.
 10. A packaged explosive composition according to claim 9 wherein said extractor is an oil.
 11. A packaged explosive composition according to claim 9 wherein said solvent is selected from the group consisting of fuel oil, mineral oil, lubricating oil, kerosene, nitroalkanes from C1 to C3, and nitroglycerine.
 12. A packaged explosive composition according to claim 1 wherein said polyvinyl chloride film is at least 4 mils and less than 50 mils thick.
 13. A packaged explosive composition according to claim 11 wherein said polyvinyl chloride film is about 6 to about 20 mils thick.
 14. A packaged explosive composition according to claim 1 wherein said explosive composition contains about 0.1 to about 80 percent extractor.
 15. A packaged explosive composition according to claim 14 wherein said explosive composition contains about 1 to about 10 percent extractor. 